US20070221093A1 - Hydroxyapatite-forming dental material with bioactive effect - Google Patents

Hydroxyapatite-forming dental material with bioactive effect Download PDF

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Publication number
US20070221093A1
US20070221093A1 US11/687,937 US68793707A US2007221093A1 US 20070221093 A1 US20070221093 A1 US 20070221093A1 US 68793707 A US68793707 A US 68793707A US 2007221093 A1 US2007221093 A1 US 2007221093A1
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Prior art keywords
dcpa
dental material
ttcp
hydroxyapatite
dicalcium phosphate
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US11/687,937
Inventor
Albert Erdrich
Marcus Hoffmann
Andreas Piotrowski
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Kulzer GmbH
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Heraeus Kulzer GmbH
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Assigned to HERAEUS KULZER GMBH reassignment HERAEUS KULZER GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PIOTROWSKI, ANDREAS DR., ERDRICH, ALBERT DR., HOFFMAN, MARCUS DR.
Publication of US20070221093A1 publication Critical patent/US20070221093A1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/838—Phosphorus compounds, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/864—Phosphate cements

Definitions

  • the invention relates to a self-curing hydroxyapatite-forming 2-component dental material with bioactive effect.
  • the hard tissue of human teeth consists mostly of the inorganic calcium phosphate compound, hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 ).
  • hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2
  • filling materials based on different materials are available (e.g. amalgam, composites, glass ionomer cements). Although these ideally show biocompatible behavior in the tooth, usually there are no interactions between the healthy hard tissue of the tooth and the filling material.
  • the powder components of these products consist of dicalcium phosphate anhydrate (DCPA) and tetracalcium phosphate (TTCP).
  • DCPA dicalcium phosphate anhydrate
  • TTCP tetracalcium phosphate
  • a sodium monophosphate solution is used for preparation of the paste by mixing.
  • the cement of the two products attains a compressive strength of approx. 60 and 30 MPa, respectively, after curing.
  • WO 94/20064 “Calcium phosphate hydroxyapatite precursor and methods for making and using the same” (inventors: L. J. Chow and S. Takagi) describes a calcium phosphate cement based on a TTCP with a Ca:P ratio of ⁇ 2 and on another poorly soluble calcium phosphate salt, including DCPA. This cement is prepared by mixing with an 0.25 mmol/l H 3 PO 4 solution and affords compressive strengths of 60 MPa. Moreover, proteins, fillers, vaccination germs, and viscosity-altering substances can be added. The materials is said to be suitable as dental filling material, remineralization substance, desensitizer, and bone replacement material.
  • WO 2004/103419 (inventors: J. Barralet, U. Gbureck, and R. Thull) relates to a calcium phosphate cement consisting of two powder components, whereby the first component has a particle diameter of d 50 (comp1) ⁇ 15 ⁇ m and the second component has a particle diameter of d 50 (comp2)>d 50 (comp1).
  • Component 2 is 1.5- to 10-fold larger than component 1 .
  • An oligocarboxylic acid e.g. trisodium citrate, disodium malate, disodium tartrate
  • An example specifies a cement made of the components, TTCP and DCPA, with sodium phosphate being added to its powder component as an accelerator of the setting reaction. This cement attains high compressive strength ( ⁇ 100 MPa).
  • bioactive is mainly understood to refer to the capability of remineralization.
  • the goal of remineralization is to deposit hydroxyapatite [(Ca 5 (PO 4 ) 3 OH)] such that it is taken up by the hard substance of the tooth.
  • Remineralization is aimed to prevent further disintegration of the tooth and regenerate the substance of the tooth.
  • the components are designed for preparation by mixing of a paste for application directly in the cavity.
  • the paste cures therein by forming a new phase consisting mostly of hydroxyapatite (>95 wt-%). Since the composition is equal to that of the tooth, this filling material is capable of remineralization, which is also a capability of dental enamel.
  • DCPA dicalcium phosphate anhydrate
  • DCPD dicalcium phosphate dihydrate
  • TTCP tetracalcium phosphate
  • FIGS. 1 , 2 Crystal shape of the special DCPA for the synthesis of the TTCP and in the powder mixture of the paste.
  • FIG. 3 Surface of the cured paste after 24 h.
  • FIGS. 4 , 5 Remineralized surface of a test body after 44 weeks of exposure to artificial saliva (in-vitro experiment).
  • FIG. 6 Filling made of the cured paste in the natural tooth after 4 months of use, formation of a remineralized layer extending from the filling to the tooth (in-vivo experiment).
  • the DCPA is characterized by its purity with respect to the elements, iron (Fe) and manganese (Mn). The fraction of these substances must be less than 0.2 m % (200 ppm). Moreover, it must be very crystalline and form the crystal shape of small plates typical of brushite.
  • the FIGS. 1 and 2 show scanning electron microscope images of the crystal morphology of the DCPA crystallites.
  • the TTCP synthesis is carried out according to known methods, such as described, for example, in WO9420064, except that the special DCPA described above is utilized for this purpose.
  • An exemplary synthesis is described in the following:
  • the paste can be obtained by mixing the powder mixture made of DCPA and TTCP with an aqueous solution of Na 4 -EDTA or Na 5 -pentetate (400-700 mmol/l are useful).
  • the complexing agents are added to improve the preparation by mixing of the paste and for processing in the dental application (application inside the cavity, carving).
  • the paste cures with the hydroxyapatite particles forming a stronger bond than upon preparation-by-mixing using a Na 3 -citrate solution, which does not lead to higher compressive strength, but shows higher abrasion stability.
  • this property is quite important for a filling to be stabile.
  • FIG. 3 shows the surface of a test body 24 h after the preparation. During storage of the test bodies in artificial saliva, remineralization led to the formation of a new structure ( FIGS. 4 and 5 ). The shapeless particles are rearranged into prismatic structures that “grow” into the test body perpendicular to its surface, similar to enamel.
  • One advantage of the material according to the invention as compared to previously known systems is its high compressive strength combined with high abrasion stability.
  • Known systems are mainly used in the area of bone replacement materials, in which the property of “abrasion stability” is not a crucial criterion.
  • Another advantage of the material presented herein is that it is capable of remineralization. It was successfully shown in in-vitro and also in in-vivo experiments, that the material forms a new structure due to remineralization. Since the paste cures without changing its shape (no shrinkage and no expansion), no marginal gap between tooth and filling material is formed. Moreover, the filling mineralizes onto the healthy tissue of the tooth ( FIG. 6 : section of tooth 4 months after placement of the filling, in-vivo experiment).
  • a DCPA with a particle diameter (d 50 ) of 10-12 ⁇ m is used for synthesis of the TTCP. It is mixed with calcium carbonate (CaCO 3 ) at an equimolar ratio and subjected to tempering at 1400-1550° C. for 4-18 h. Once the reaction time is elapsed, the TTCP generated is removed from the furnace at the temperature of synthesis and then cooled at room temperature. For use in the powder mixture, the particle size (d 50 ) is adjusted to a diameter of 9-18 ⁇ m by trituration in a ball triturator.
  • the DCPA in the powder mixture of the paste has a particle size of 0.5-3 ⁇ m and still possesses its plate-shaped crystal structure. Ideally, the particle size of the TTCP and DCPA is 10 ⁇ m and 1 ⁇ m, respectively.
  • a paste is obtained by mixing the powder mixture made of DCPA and TTCP with an aqueous Na 4 -EDTA solution (500 mmol/l).
  • the long-term stability of the cured paste was in excess of 1 year.
  • the abrasion stability was investigated using the ACTA machine according to De Gee 23 , 4 (De Gee, A. J., Pallav, P., Davidson, C. L.: Effect of abrasion medium on wear of stress-bearing composites and amalgam in vitro. J Dent Res 65, 654-658 (1986)).
  • the paste according to the invention showed lower abrasion by a factor of two-thirds than the system according to WO 2004/103419.

Abstract

The invention relates to a self-curing two-component dental material having as its components A powder component containing dicalcium phosphate anhydrate (DCPA) or dicalcium phosphate dihydrate (DCPD) and tetracalcium phosphate (TTCP) and B liquid component containing water and complexing agent, whereby crystalline DCPA having a crystal shape of small plates typical of brushite having an iron (Fe), manganese (Mn), molybdenum (Mo), and tungsten (W) content of less than 0.2 m % (200 ppm) each is used.

Description

  • The invention relates to a self-curing hydroxyapatite-forming 2-component dental material with bioactive effect.
  • The hard tissue of human teeth consists mostly of the inorganic calcium phosphate compound, hydroxyapatite (Ca10(PO4)6(OH)2). For replacement, a multitude of filling materials based on different materials are available (e.g. amalgam, composites, glass ionomer cements). Although these ideally show biocompatible behavior in the tooth, usually there are no interactions between the healthy hard tissue of the tooth and the filling material.
  • Products for craniofacial surgery are on offer1 that resemble human bone material. They are characterized by their biocompatibility, i.e. the materials are substituted own bone of the patient. Osteoclastic absorption and new bone formation in the body eventual lead to a gradual conversion to bone.
    1 Bone Source made by Leibinger Stryker, Norian CRS made by Synthes-Stratec
  • The powder components of these products consist of dicalcium phosphate anhydrate (DCPA) and tetracalcium phosphate (TTCP). A sodium monophosphate solution is used for preparation of the paste by mixing. The cement of the two products attains a compressive strength of approx. 60 and 30 MPa, respectively, after curing.
  • WO 94/20064 “Calcium phosphate hydroxyapatite precursor and methods for making and using the same” (inventors: L. J. Chow and S. Takagi) describes a calcium phosphate cement based on a TTCP with a Ca:P ratio of<2 and on another poorly soluble calcium phosphate salt, including DCPA. This cement is prepared by mixing with an 0.25 mmol/l H3PO4 solution and affords compressive strengths of 60 MPa. Moreover, proteins, fillers, vaccination germs, and viscosity-altering substances can be added. The materials is said to be suitable as dental filling material, remineralization substance, desensitizer, and bone replacement material.
  • WO 2004/103419 (inventors: J. Barralet, U. Gbureck, and R. Thull) relates to a calcium phosphate cement consisting of two powder components, whereby the first component has a particle diameter of d50(comp1)<15 μm and the second component has a particle diameter of d50(comp2)>d50(comp1). Component 2 is 1.5- to 10-fold larger than component 1. An oligocarboxylic acid (e.g. trisodium citrate, disodium malate, disodium tartrate) is added to the mixing liquid in order to reduce the zeta-potential of the particles, which serves the purpose of improving the preparation-by-mixing properties of powder and liquid. An example specifies a cement made of the components, TTCP and DCPA, with sodium phosphate being added to its powder component as an accelerator of the setting reaction. This cement attains high compressive strength (˜100 MPa).
  • It is the object of the invention to provide another dental material with a bioactive effect. The term, “bioactive”, is mainly understood to refer to the capability of remineralization. The goal of remineralization is to deposit hydroxyapatite [(Ca5(PO4)3OH)] such that it is taken up by the hard substance of the tooth. Remineralization is aimed to prevent further disintegration of the tooth and regenerate the substance of the tooth.
  • This object is met according to the invention by a self-curing 2-component dental material having as its components
    • powder component containing
      • dicalcium phosphate anhydrate (DCPA) or dicalcium phosphate dihydrate (DCPD)
      • tetracalcium phosphate (TTCP) and
    • liquid component containing
      • water
      • complexing agent from the group of Na4-EDTA or Na5-pentetate,
        whereby crystalline DCPA having a crystal shape of small plates typical of brushite having an iron (Fe), manganese (Mn), molybdenum (Mo), and tungsten (W) content of less than 0.2 m % (200 ppm) each is used.
  • The components are designed for preparation by mixing of a paste for application directly in the cavity. The paste cures therein by forming a new phase consisting mostly of hydroxyapatite (>95 wt-%). Since the composition is equal to that of the tooth, this filling material is capable of remineralization, which is also a capability of dental enamel.
  • The special dicalcium phosphate anhydrate (DCPA) or dicalcium phosphate dihydrate (DCPD) of the invention is needed to have a particularly reactive paste. It is used also in the synthesis of the tetracalcium phosphate (TTCP) employed here.
    • LIST OF FIGURES
  • FIGS. 1, 2: Crystal shape of the special DCPA for the synthesis of the TTCP and in the powder mixture of the paste.
  • FIG. 3: Surface of the cured paste after 24 h.
  • FIGS. 4, 5: Remineralized surface of a test body after 44 weeks of exposure to artificial saliva (in-vitro experiment).
  • FIG. 6: Filling made of the cured paste in the natural tooth after 4 months of use, formation of a remineralized layer extending from the filling to the tooth (in-vivo experiment).
  • The DCPA is characterized by its purity with respect to the elements, iron (Fe) and manganese (Mn). The fraction of these substances must be less than 0.2 m % (200 ppm). Moreover, it must be very crystalline and form the crystal shape of small plates typical of brushite. The FIGS. 1 and 2 show scanning electron microscope images of the crystal morphology of the DCPA crystallites.
  • The TTCP synthesis is carried out according to known methods, such as described, for example, in WO9420064, except that the special DCPA described above is utilized for this purpose. An exemplary synthesis is described in the following:
  • The paste can be obtained by mixing the powder mixture made of DCPA and TTCP with an aqueous solution of Na4-EDTA or Na5-pentetate (400-700 mmol/l are useful). The complexing agents are added to improve the preparation by mixing of the paste and for processing in the dental application (application inside the cavity, carving).
  • Moreover, the paste cures with the hydroxyapatite particles forming a stronger bond than upon preparation-by-mixing using a Na3-citrate solution, which does not lead to higher compressive strength, but shows higher abrasion stability. For application as a direct filling material, this property is quite important for a filling to be stabile.
  • The bioactive effect of the cured paste was successfully demonstrated by means of in-vitro experiments. FIG. 3 shows the surface of a test body 24 h after the preparation. During storage of the test bodies in artificial saliva, remineralization led to the formation of a new structure (FIGS. 4 and 5). The shapeless particles are rearranged into prismatic structures that “grow” into the test body perpendicular to its surface, similar to enamel.
  • One advantage of the material according to the invention as compared to previously known systems is its high compressive strength combined with high abrasion stability. Known systems are mainly used in the area of bone replacement materials, in which the property of “abrasion stability” is not a crucial criterion. Application of the material as a dental filling material, though, necessitates stability with respect to mastication stress.
  • Another advantage of the material presented herein is that it is capable of remineralization. It was successfully shown in in-vitro and also in in-vivo experiments, that the material forms a new structure due to remineralization. Since the paste cures without changing its shape (no shrinkage and no expansion), no marginal gap between tooth and filling material is formed. Moreover, the filling mineralizes onto the healthy tissue of the tooth (FIG. 6: section of tooth 4 months after placement of the filling, in-vivo experiment).
  • The following example demonstrates one embodiment of the invention:
    • EXAMPLE
  • A DCPA with a particle diameter (d50) of 10-12 μm is used for synthesis of the TTCP. It is mixed with calcium carbonate (CaCO3) at an equimolar ratio and subjected to tempering at 1400-1550° C. for 4-18 h. Once the reaction time is elapsed, the TTCP generated is removed from the furnace at the temperature of synthesis and then cooled at room temperature. For use in the powder mixture, the particle size (d50) is adjusted to a diameter of 9-18 μm by trituration in a ball triturator. The DCPA in the powder mixture of the paste has a particle size of 0.5-3 μm and still possesses its plate-shaped crystal structure. Ideally, the particle size of the TTCP and DCPA is 10 μm and 1 μm, respectively.
  • A paste is obtained by mixing the powder mixture made of DCPA and TTCP with an aqueous Na4-EDTA solution (500 mmol/l).
  • After curing, the material is subjected to testing in accordance with ISO 9917:2004. Compressive strength values of 90 MPa+/−7 MPa are thus obtained.
  • The long-term stability of the cured paste was in excess of 1 year.
  • The abrasion stability was investigated using the ACTA machine according to De Gee23, 4 (De Gee, A. J., Pallav, P., Davidson, C. L.: Effect of abrasion medium on wear of stress-bearing composites and amalgam in vitro. J Dent Res 65, 654-658 (1986)). In the process, the paste according to the invention showed lower abrasion by a factor of two-thirds than the system according to WO 2004/103419.

Claims (2)

1. Self-curing dental material comprising
A) powder component comprising i) dicalcium phosphate anhydrate (DCPA) or dicalcium phosphate dehydrate (DCPD) and ii) tetracalcium phosphate (TTCP) and
B) liquid component comprising water and a complexing agent,
wherein the DCPA has a crystal shape of small plates and wherein iron (Fe), manganese (Mn), molybdenum (Mo), and tungsten (W) are each present in the DCPA in an amount of less than 0.2 m % (200 ppm).
2. Dental material according to claim 1, wherein the complexing agent is selected from the group consisting of Na4-EDTA and Na5-pentetate.
US11/687,937 2006-03-23 2007-03-19 Hydroxyapatite-forming dental material with bioactive effect Abandoned US20070221093A1 (en)

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DE102006013854.6 2006-03-23
DE102006013854A DE102006013854B4 (en) 2006-03-23 2006-03-23 Use of a hydroxyapatite-forming material having a bioactive effect as a dental material

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EP (1) EP1837006B1 (en)
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BR (1) BRPI0701285A (en)
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DE (1) DE102006013854B4 (en)
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MX (1) MX2007003352A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100121459A1 (en) * 2008-11-12 2010-05-13 Garigapati Venkat R Tetra Calcium Phosphate Based Organophosphorus Compositions and Methods
US8765189B2 (en) 2011-05-13 2014-07-01 Howmedica Osteonic Corp. Organophosphorous and multivalent metal compound compositions and methods
USRE45561E1 (en) * 2003-05-23 2015-06-16 Ortus Medical Limited Calcium phosphate bone cements
US9168114B2 (en) 2013-10-17 2015-10-27 B & D Dental Corp. Method of making a dental prosthesis
US9265857B2 (en) 2010-05-11 2016-02-23 Howmedica Osteonics Corp. Organophosphorous, multivalent metal compounds, and polymer adhesive interpenetrating network compositions and methods
WO2018031586A1 (en) * 2016-08-08 2018-02-15 Launchpad Medical, Llc Compositions and methods for adhesion to surfaces
CN114618013A (en) * 2022-03-10 2022-06-14 苏州卓恰医疗科技有限公司 MnO2Modified magnesium-based bone cement powder, bone cement and preparation method thereof

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US3679360A (en) * 1970-06-26 1972-07-25 Nasa Process for the preparation of brushite crystals
US5342441A (en) * 1991-06-26 1994-08-30 Nitta Gelatin Inc. Biologically compatible hardening material for dental or medical applications
US20020009693A1 (en) * 2000-06-13 2002-01-24 Pelerin Joseph J. Dental restoration solution for root and dentinal tubule treatment and a method for use thereof
US20050271741A1 (en) * 2000-07-13 2005-12-08 Cana Lab Corporation Injectable calcium phosphate cements and the preparation and use thereof

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GB1450157A (en) * 1973-03-06 1976-09-22 Colgate Palmolive Co Dental powder cement and filling material
JP3668530B2 (en) * 1995-07-27 2005-07-06 太平化学産業株式会社 Method for producing tetracalcium phosphate
JPH09103478A (en) * 1995-10-11 1997-04-22 Nitta Gelatin Inc Hardenable material for medical or dental purpose
US6383519B1 (en) * 1999-01-26 2002-05-07 Vita Special Purpose Corporation Inorganic shaped bodies and methods for their production and use
US7294187B2 (en) * 2001-01-24 2007-11-13 Ada Foundation Rapid-hardening calcium phosphate cement compositions
GB0311846D0 (en) * 2003-05-23 2003-06-25 Univ Birmingham High strength and injectable apatitic calcium phosphate cements
US7459018B2 (en) * 2005-04-08 2008-12-02 Howmedica Leibinger Inc. Injectable calcium phosphate cement

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Publication number Priority date Publication date Assignee Title
US3679360A (en) * 1970-06-26 1972-07-25 Nasa Process for the preparation of brushite crystals
US5342441A (en) * 1991-06-26 1994-08-30 Nitta Gelatin Inc. Biologically compatible hardening material for dental or medical applications
US20020009693A1 (en) * 2000-06-13 2002-01-24 Pelerin Joseph J. Dental restoration solution for root and dentinal tubule treatment and a method for use thereof
US20050271741A1 (en) * 2000-07-13 2005-12-08 Cana Lab Corporation Injectable calcium phosphate cements and the preparation and use thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE45561E1 (en) * 2003-05-23 2015-06-16 Ortus Medical Limited Calcium phosphate bone cements
US20100121459A1 (en) * 2008-11-12 2010-05-13 Garigapati Venkat R Tetra Calcium Phosphate Based Organophosphorus Compositions and Methods
US8232327B2 (en) 2008-11-12 2012-07-31 Howmedia Osteonics Corp Tetra calcium phosphate based organophosphorus compositions and methods
US8273803B2 (en) 2008-11-12 2012-09-25 Howmedica Osteonics Corp. Tetra calcium phosphate based organophosphorus compositions and methods
US9265857B2 (en) 2010-05-11 2016-02-23 Howmedica Osteonics Corp. Organophosphorous, multivalent metal compounds, and polymer adhesive interpenetrating network compositions and methods
US10286102B2 (en) 2010-05-11 2019-05-14 Howmedica Osteonics Corp Organophosphorous, multivalent metal compounds, and polymer adhesive interpenetrating network compositions and methods
US8765189B2 (en) 2011-05-13 2014-07-01 Howmedica Osteonic Corp. Organophosphorous and multivalent metal compound compositions and methods
US9168114B2 (en) 2013-10-17 2015-10-27 B & D Dental Corp. Method of making a dental prosthesis
WO2018031586A1 (en) * 2016-08-08 2018-02-15 Launchpad Medical, Llc Compositions and methods for adhesion to surfaces
EP3496729A4 (en) * 2016-08-08 2020-10-07 Launchpad Medical, Inc Compositions and methods for adhesion to surfaces
US11247941B2 (en) 2016-08-08 2022-02-15 RevBio, Inc. Compositions and methods for adhesion to surfaces
CN114618013A (en) * 2022-03-10 2022-06-14 苏州卓恰医疗科技有限公司 MnO2Modified magnesium-based bone cement powder, bone cement and preparation method thereof

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JP5162146B2 (en) 2013-03-13
DE102006013854A1 (en) 2007-09-27
EP1837006B1 (en) 2015-05-06
EP1837006A3 (en) 2008-06-25
ES2542990T3 (en) 2015-08-13
MX2007003352A (en) 2009-02-16
JP2007254472A (en) 2007-10-04
DE102006013854B4 (en) 2010-08-19
EP1837006A2 (en) 2007-09-26
BRPI0701285A (en) 2007-11-27

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